Amine salts of dinitrophenols



Patented Oct. 2, .1945

UNITED STATES PATENT OFFICE} AMINE SALTS OF DINITROPHENOLS Frank B. Smith and John N. Hansen, Midland,

Mich, assignors to The Dow Chemical oolnpally, Midland, Mich, a corporation of Michigan No Drawing. Application April 30, 1941,

Serial No. 391,099

2 Claims. (Cl. 260-583) This invention relates to amine salts of phenols and is particularly concerned with the addition products of dinitrophenols with amines of the alkylene-diamine and polymethylene-diamine type having the following formula: I

reactants employed. The expression monosalt as herein employed refers to an alkylene- 'dialnine addition compound with a dinitrophenol in which but one molecule of the phenol is associated with eachalkylene-diamine molecule. The expression di-salt refers to amine addition salts in' which 2 molecules of the di-' nitro-phenol are associated with each molecule of the alkylene-diamine.

In carrying out the reaction any suitable amounts of reactants may be employed. It has been found that the mono-salt is obtained in good yield when equilnolecular proportions of the dinitro-phenol and the amine or an excess of the amine is employed. The di-salt is obtained in good yield and as the primary product of reaction when at least two molecular proportions of dinitro-phenol are employed for each solids diflicultly soluble in water and somewhat soluble in many common organic solvents. These compounds are stable to light and air, not appreciably affected by carbon dioxide and are yellow to orange-red in color. Preferred groups of amine salts are obtained from those dinitrophenols characterized by nuclear substituted nitro groups in the para position and in one of the positions ortho to the hydroxyl.

A group of compounds falling within the scope of the invention as defined above which are particularly valuable for use in insecticidal and fungicidal spray and dust compositions are those alkylene-diamine salts derived from 2.4- dinitrophenols having the formula:

wherein Y represents an aryl, cycloalkyl, aralkyl,

or alkyl radical or hydrogen.

The new compounds are prepared by reacting a suitable amine compound such as ethylenebe formed depending upon the proportions of proportion of the amine. Where an unreacted excess of one or the other reactant is present in the final product, separation is readily accomplished by extraction of thecrude amine addition salt product with benzene or other ,selective solvent for the dinitro-phenol or amine and in which the amine salt is diflicultly soluble.

The operating temperatures employed in the reaction are not critical, although reduced amounts of solvents are required at somewhat elevated temperatures, e. gpbetween about 40 and 120 C. and conveniently at the boiling temperature of the reaction mixture. While the reactants and solvent may simply be mixed together, a convenient method of operation comprises adding a solution of one reactant to the other. To insure the formation of a relatively homogeneous product and to minimize occlusion, the amine is preferably added portionwise with stirring to a solution of the dinitro-phenol over a short period of time. Following completion of the reaction, themixture is filtered or otherwise manipulated to separate out the amine salt which may be further purified by washing with small amounts of organic solvents as described above or by recrystallization. The amine salt obtained is then'dried at a temperature calculated to volatilize residual traces oi solvent.

The following examples set forth certain embodiments of the invention, but are' not to be constructed as limiting the same.

Example 1 26.6 grams (0.1 mol) of 2.4-dinitro-6-cyclohexyl-phenol was dissolved in 30 milliliters of hot benzene and 6.0 grams diamine added pol-tionwise thereto with stirring.

(0.1 mol) of ethylene- The mixture was warmed and stirred at 60-80 I milliliters oi! hot alcohol and reacted with C., an addition salt of the amine and phenol aseaaea' precipitating from solution. The mixture wasthen cooled and filtered to obtain a residue of 32 grams of the ethylene-diamine mono-saltof 2.4-dinitro-6-cyclohexyl-phenol as a .yel1ow crystalline solid melting at 19l-l92 C. This compound was soluble to the extent of 0.025 gram per 100 grams of water at 25 C. The pH of the saturated water. solution was 9.12.

Example 2 79.8 grams (0.3 mol) 2.4-dinitr0-8-cyclohexyl-phenol was dissolved in 100 milliliters of hot benzene and 57.6 grams (0.226 moi) of N.N'-di- (2-methyl-cyclohexyl) -ethylene dlamine added portionwise thereto over a period of minutes.

and at a temperature ranging between 60 and 80 C. The reaction mixture was heated and stirred for'an additional 15yto minutes and thereafter cooled and filtered to obtain the amine di-saltas a yellow crystalline residue. This crude product was washed with cold benzene and dried at 70 C ..to obtain the N.N'-di-(2-methyl-cyclo hexyl) -ethylene-diamine di-salt of 2.4-dinitro-6- cyclohexyl-phenol melting at 205-207 C. This compound was soluble to the extent of 0.0056 gram per 100 grams of water at C. The saturated water solution had a pH of 8.4.

' The N.N-di- (2-methyl-cyclohexyl) -ethylenediamine herein employed is a viscous liquid boiling at 165 C; at 8 millimeters pressure and having a specific gravity of 0.92 at 20l4 C. This compound is prepared by reacting 2-methyl-cyclohexyl-amine with ethylene chloride or ethylene bromide under conditions of elevated temperature and ressure and neutralizing the resultant amine hydrohalide with aqueous sodium hydroxide.

Esample 8 mol) of propylene-diamine were reacted together 1.6-diamino-hexane.

'diamines may be employed v amples to obtain addition salts of the dinitrotion mixture was heated and stirred for approximately Va hour and thereafter cooled and filtered and the crystalline residue washed with alcohol.

The residue from the alcohol washing was dried at 70 vC. to obtain 55.5 grams :0! propylene-diamine di-saltoi 2.4 -dinitro-6 phenyl-phenol as a a yellow crystalline product'melting at 1935 195? C. This compound is soluble to the extent of 0.254: gram per 100 grams of water to give a saturated solution having a pH of 7.4.

Example 6 53.2 grams (0.2 moi) of 2.4-dinitro-6-cyclohexyl-phenol was dissolved in 200 milliliters of boiling ethanol and 10.4 grams (0.1 mol) of N-(2'- hydroxy-ethyl) -ethylene-diamine added portionwise thereto with Heat of reaction was evolved and a crystalline precipitate formed. After all of the amine had been added, the mixture was cooled to room temperature and filtered. The residue from the illtration was recrystallized from hot ethanol and air dried to obtain 48 grams of N-(Z-hydroxyethyl) -ethy1ene-diamine di-salt of 2.4-dinitro-6- cyclohexyl-phenol as a yellow crystalline com- P und melting at 160-163.5 C;

Other alkylene-diamines and polymethyleneas shown in the exphenols. Representative of such amine compounds are N.N'-dl-isobutenyl-ethylene=diamine,

1.4-diamino-butane, 1.10- diamino-decan'e 1.6 diamino 3 tertiarybutylhexane, 1.8-diam'ino-octane, 1.6-diamino-2.5-

dimethyl-hexane, heptamethylene-diamine, bu-

- tylene-diamlne, N-cyclohexyl-ethylene-diamine,

- yl) -hexamethflene-diamine,

in the presence oi. 50 milliliters of benzene and at a temperature of 50' C. The reacted mixture was cooled, and filtered, and the residue washed with cold benzene to obtain 50.5 grams of the propylene-diamine mono-salt oi 2.4-dinitro-6- methyl-phenol as a yellow crystalline compound melting at Fir-174 C. This compound was soluhis in water to the extent of 0.567 gram per 100 grams of water at 25 C. The saturated water solution had a pH of 9.8.

Example I amine, NN'-dipropyl-iethylene-diamine,

the dinitroephenols shown in the exam- N-(3-hydroxy-propyl)-ethylene-diamine, N.N'- dibenzyl-butylene-diamine, N-(beta-phenyleth- N.N'-diethyl-octamethylene-diamine, N isobutyl propylene di etc. In

place of ples other representative compounds such as 2.4- dinitro-phenol, 2.4-dinitro-G-ethyl-phenol, 2.4-dinitro-G-n-hexyl-phenol, 2.4-dinitro 6 n octylphenol, 2.4-dinitro-6-benzyl-phenol, 2.4-dinitro- G-cyclopentyl-phenol,

the like may be employed.

The alkylenevdiamine and the diamine addition salts of dinitro-phenols as set 39.0, grams (oz moi) of 2.4-dinitro-0-methylphenol was dissolved in 50 milliliteraoi boilin benzene and 25.2 grams (0.1 mol) of NJV-dl- (z-methyl-cyclohexyl)-ethylene-diamine added portionwise thereto substantially as described in Example 2. After heating and stirring for some Immple 5 In a simllarmanner 52 grams (0.2 moi) of 2.4dinitro-5-phenyl-phenoi was dissolved in.850 7.4

grams (0.1 moi) of propylene diamine. The reacv positions for th control forth in the preceding examples may be used as active toxicants in either spray or duct comof plant parasites. While many of these compounds exert a fungicidal action, others have been found particularly well adapted for use in insecticidal compositions.

when employed in dust mixtures. the amine salts are preferably dispersed in and on solid, finely divided, inert carriers such as diatomaceous earth, volcanic ash, bentonite, talc, finely dividedwood flour. and thelike. For dusting purposes, compositions comprising from about 0.5 to 5 per centby weight 0! the amine salt are such aqueous compositions.

particularlyuselul. 1

Dispersions oi the salts on or in inert carriers may alsobe employed in water suspension as agricultural sprays for dormant or summer application to growing trees or aseradicant fungicides. In preparing dust mixtures for use in be employed in amount 'u'p weight of the finely divided-solid concentrate.

stirring over a short period.

2.4-dinitro-6-chloro-phe- I nol, 2.6-dinitro-4-methyl-phenol, 2.5-dinitro-4- cyclohexyl-phenol, 2.4-dinitro-5-naphthylamino- I phenol, 2.4-dinitro-5-ortho-toluidino-phencl and polymethylene- Ethylene-diamine mono-salt of assume although from is m as per cent by'weight is preferred. Similarly, aqueous solutions ,or dis-' persions of the amine salts are useful in per.

site control.

Various wetting sticking, and dispersing al ents such as glyceryl oleate, alkali metal cas'einates.

aluminum naphthenate, alkali metal salts of 1 aromatic hydrocarbons and phenols, sodium 'lauryl sulfate, partially neutralized sulfuric acid derivatives of fatty acids and oils, blood albumen,-

soap, and the like may be employed in combination with .the new amine salts. Similarly the amine salts can be combined with other insecticidal and fungicidal agents such as petroleum, fish and vegetable oils, lead arsenate, sulfur, copper sprays, and the like for the oontrolof'various insect and fungous pests.

A representative composition found valuable for the-control of agricultural parasites is the following:

The foregoing materials were ground and mixed together and applied in the amount of 1.5 pounds I per 100 gallons of water toplants'infested with, the adults and young of red spiders. Within 24 hours after application a 100 per cent kill of the spiders was obtained.

Among the compounds withwhich the present. invention is particularly concerned are those hav-:

ing the following general formula:

NO: as I Parts: by :weight droz e n, n 'isaninteger, greater than 2.

wherein a, Y. and nare as set forth above. Similarly the (ii-salts may Y I 1; 1m alkylenediamin'e salt or zi-dinltro ilwherein R. represents a member of the" group consisting of alkyl, alkenyl, hydroxy-alhl, oyclo-.

alhrl, and arallgvl radicals and hydrogen, Y represents a member of the group consisting of aryl,

cycloalkyl, aralkyl, and alkyl radicals and hy- I I and'w 'is an inteser not Mono-salts falling withinthis groupie! compounds have the probable formula:

having the formula:

in which R, Y, and hare as previously-identified.

We claim:

cyclohexyl-phenol having the formula' wherein n is an'integer, and w is an integer not greater than 2. 2. The ethylenediamine mono-salt of 24 dinitro-ii-c'yclohexyl-phenol having the formula B. sm'm. Jorm N. menu.

identified as those 

